Mixtures containing 1.1.1.4.4.4.- hexafluorobutene  and 1-chloro-3.3.3-trifluoropropene

ABSTRACT

The present invention relates to mixtures of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and 1-chloro-3,3,3-trifluoropropene (1233zd). The blends are useful as blowing agents for polymer foam, solvents, aerosol propellants and heat transfer media.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 15/651,848,filed Jul. 17, 2017, which is a division of U.S. application Ser. No.14/868,222, filed Sep. 28, 2015 (now U.S. Pat. No. 9,708,454), whichapplication is a division of U.S. application Ser. No. 13/276,369 filedNov. 19, 2011, (now U.S. Pat. No. 9,145,480, issued Sep. 29, 2015),which application is related to and claims the priority benefit of U.S.provisional application No. 61/407,708 filed Oct. 28, 2010, the contentsof which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to mixtures of1,1,1,4,4,4-hexafluorobutene (1336mzzm) and1-chloro-3,3,3-trifluoropropene (1233zd). More particularly, the presentinvention relates to blowing agent compositions containing1,1,1,4,4,4-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene.

BACKGROUND OF THE INVENTION

The class of foams known as low density rigid polyurethane orpolyisocyanurate foam has utility in a wide variety of insulationapplications including roofing systems, building panels, refrigeratorsand freezers. A critical factor in the large-scale commercial acceptanceof rigid polyurethane foams in the building insulation industry has beentheir ability to provide a good balance of properties. Rigidpolyurethane and polyisocyanurate foams are known to provide outstandingthermal insulation, excellent fire properties and superior structuralproperties at reasonably low densities.

The methods of producing polyurethane and polyisocyanurate foams areknown and consist in general of the reaction of an organicpolyisocyanurate (including diisocyanate) and a polyol or mixture ofpolyols in the presence of a volatile blowing agent, which is caused tovaporize by the heat liberated during the reaction of isocyanate andpolyol. This reaction can be enhanced through the use of amine and/orother catalysts as well as surfactants. The catalysts ensure adequatecuring of the foam, while the surfactants regulate and control cellsize. Flame-retardants are traditionally added to rigid polyurethane orpolyisocyanurate foam to reduce its flammability.

The foam industry has historically used liquid fluorocarbon blowingagents such as trichlorofluoromethane (CFC-11) and1,1-dichloro-1-fluoroethane (HCFC-141b) because of ease of use inprocessing conditions. Fluorocarbons act not only as blowing agents byvirtue of their volatility, but also are encapsulated or entrained inthe closed cell structure of the rigid foam and are the majorcontributor to the low thermal conductivity properties of rigid urethanefoams.

The use of a fluorocarbon as the preferred commercial expansion orblowing agent in insulating foam applications is based in part on theresulting k-factor associated with the foam produced. K-factor isdefined as the rate of transfer of heat energy by conduction through onesquare foot of one inch thick homogenous material in one hour wherethere is a difference of one degree Fahrenheit perpendicularly acrossthe two surfaces of the material. Since the utility of closed-cellpolyurethane-type foams is based, in part, upon their thermal insulationproperties, it would be advantageous to identify materials that producelower k-factor foams than those above.

Many such blowing agents currently used for thermoset foams(PUR/PIR/Phenolic) also suffer from environmental or performancedisadvantages. Concern has increased in recent years about potentialdamage to the earth's atmosphere and climate, and certain chlorine-basedcompounds have been identified as particularly problematic in thisregard. The use of chlorine-containing compositions (such aschlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and thelike) has become generally disfavored because of the ozone-depletingproperties associated with many of such compounds. There has thus beenan increasing need for new fluorocarbon and hydrofluorocarbon compoundsand blends of existing compositions that offer alternatives for foamingapplications. Blowing agents with above atmospheric boiling pointscharacteristically have poor low temperature thermal performance. Thus,ideal blowing agents or agent blends should be a LGWP material that hasoptimal performance over a wide temperature range.

Hydrohaloolefins like 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and1-chloro-3,3,3-trifluoropropene (1233zd) are being independentlydeveloped as stand alone agents to meet these requirements. One problemassociated with 1336mzzm, however, is that it has an elevated boilingpoint and contains 6 fluorine atoms in its structure. Thus, by itself,it exhibits several of the foregoing disadvantages, which makes it lessvaluable and cost prohibitive as an agent.

Accordingly, blowing agents are desirable in the art that exhibit lowk-factor values, low global warming potential, low molecular weight,cost effective and optimal performance over a wide temperature range.The present invention addresses each of the foregoing in the embodimentsand examples provided herein.

SUMMARY OF THE INVENTION

The invention relates to mixtures comprising, consisting essentially ofor consisting of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and1-chloro-3,3,3-trifluoropropene (1233zd). In certain aspects, thecompositions comprise from about 5 to about 70 mole percent1,1,1,4,4,4-hexafluorobutene and from about 30 to about 95 mole percent1-chloro-3,3,3-trifluoropropene. The compositions may also comprise fromabout 30 to about 70 mole percent 1,1,1,4,4,4-hexafluorobutene and fromabout 30 to about 70 mole percent 1-chloro-3,3,3-trifluoropropene. Infurther embodiments, the compositions comprise from about 40 to about 60mole percent 1,1,1,4,4,4-hexafluorobutene and from about 40 to about 60mole percent 1-chloro-3,3,3-trifluoropropene. In even furtherembodiments, the compositions comprise about 50 mole percent1,1,1,4,4,4-hexafluorobutene and about 50 mole percent1-chloro-3,3,3-trifluoropropene.

Accordingly, and in one embodiment, the present invention relates toblowing agent compositions including 1,1,1,4,4,4-hexafluorobutene(1336mzzm); 1-chloro-3,3,3-trifluoropropene (1233zd); and, optionally,at least one adjuvant selected from the group consisting of co-blowingagent(s), polyol(s), surfactant(s), polymer modifier(s), colorant(s),dye(s), solubility enhancer(s), flammability suppressant(s), flameretardants(s), antibacterial agent(s), viscosity reduction modifier(s),filler(s), vapor pressure modifier(s), nucleating agent(s), catalyst(s)and combination of any two or more of these.

1,1,1,4,4,4-hexafluorobutene may be provided in any effective amount toachieve the desired effects discussed herein. In one embodiment, such aneffective amount is from about 5 to about 70 mole percent. In furtherembodiments, such an effective amount is from about 30 to about 70 molepercent; from about 40 to about 60 mole percent; or about 50 molepercent. While 1,1,1,4,4,4-hexafluorobutene may be provided as anyisomer or mixtures of isomers, as defined herein, in one embodiment thecomposition includes at least the cis isomer of 1336mzzm, which may beprovided alone or in a mixture with the trans isomer. To this end,1336mzzm may include from about 50 weight percent to about 100 weightpercent of the cis isomer and from about 0 weight percent to about 50weight percent of the trans isomer; from about 75 weight percent toabout 100 weight of the cis isomer and from about 0 weight percent toabout 25 weight percent of the trans isomer; or from about 90 weightpercent to about 100 weight percent of the cis isomer and from about 0weight percent to about 10 weight percent of the trans isomer.

1-chloro-3,3,3-trifluoropropene can similarly be provided in anyeffective amount to achieve the desired effect discussed herein. In oneembodiment, such an effective amount is from about 30 to about 95 molepercent. In further embodiments, such an effective amount is from about30 to about 70 mole percent; about 40 to about 60 mole percent; or about50 mole percent. While 1-chloro-3,3,3-trifluoropropene may be providedas any isomer or mixture of isomers, as defined herein, in oneembodiment, the composition includes at least the trans isomer of1233zd, which may be provided alone or in a mixture with the cis isomer.To this end, 1233zd may include from about 50 weight percent to about100 weight percent of the trans isomer and from about 0 weight percentto about 50 weight percent of the cis isomer; from about 75 weightpercent to about 100 weight percent of the trans isomer and from about 0weight percent to about 25 weight percent of the cis isomer; or fromabout 90 weight percent to about 100 weight percent of the trans isomerand from about 0 weight percent to about 10 weight percent of the cisisomer.

In further embodiments of the blowing agent composition, the at leastone adjuvant includes a co-blowing agent, which may include ahydrofluorocarbon (HFC) or hydrocarbon co-blowing agent. With respect tothe former, HFC co-blowing agents may include one or more C1-C4 HFCs,such as, but not limited to, difluoromethane (HFC-32), fluoroethane(HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143),tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125),pentafluoropropane (HFC-245), hexafluoropropane (HFC-236),heptafluoropropane (HFC-227), pentafluorobutane (HFC-365),hexafluorobutane (HFC-356), all isomers of all of these, andcombinations of two or more of these. With respect to the latter, suchagents may include one or more C4-C6 hydrocarbons, such as, but are notlimited to, isopentane, normal pentane, cyclopentane, butane andisobutane, and combinations of two or more of these.

Additional or alternative co-blowing agents that may be provided as anadjuvant include one or more of the following: water, CO₂, CFCs, HCCs,HCFCs, C1-C5 alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers anddiethers, organic acids, such as but not limited to formic acid, andcombinations of two or more of these.

In further embodiments, the present invention also relates to a foamablecomposition including a foam forming agent and the blowing agentcomposition, as described herein. The blowing agent may be provided as apreblend, wherein one or more of the foregoing components are firstpreblended, then provided to the foamable composition. Alternatively,each component of the blowing agent composition may be separatelyprovided to the foamable composition to form the blowing agentcomposition therewithin.

The foamable composition exhibits k-factor values that are consideredadvantageous. In one embodiment, the foamable composition exhibits aninitial (measured within 24 hours of foam preparation) k-factor (BTUin/hr ft²° F.) at 40° F. of not greater than about 0.14, and in certainembodiments, not greater than 0.138. In further embodiments, thefoamable composition exhibits an initial k-factor (BTU in/hr ft²° F.) at75° F. of not greater than about 0.16, and in certain embodiments, notgreater than 0.158. In even further embodiments, the foamablecomposition exhibits an initial k-factor (BTU in/hr ft²° F.) at 110° F.of not greater than about 0.18, and in certain embodiments, not greaterthan 0.1772.

The present invention also relates to a foam premix compositionincluding one or more polyols and the blowing agent composition, asdescribed herein. Again, the blowing agent may be provided as apreblend, wherein one or more of the foregoing components are firstpreblended, then provided to the foam premix. Alternatively, eachcomponent of the blowing agent composition may be separately provided tothe foam premix to form the blowing agent composition therewithin.

In further embodiments, the present invention also relates to a methodof forming a foam by adding to a foamable and/or foaming composition theblowing agent composition described herein and reacting the foamingcomposition under conditions effective to form a cellular structure.While not limited thereto, the foamable composition may includeisocyanate and one or more polyols. The foamable composition may alsoinclude at least one additional component selected from the groupconsisting of catalysts, surfactants, flame retardants, colorants, andcombinations of these.

In further embodiments, the present invention relates to a foamincluding a plurality of polymeric cells and the blowing agentcomposition described herein. The foam exhibits k-factor values that areconsidered advantageous. In one embodiment, the foam exhibits an initialk-factor (BTU in/hr ft²° F.) at 40° F. of not greater than about 0.14,and in certain embodiments, not greater than 0.138. In furtherembodiments, the foam exhibits an initial k-factor (BTU in/hr ft²° F.)at 75° F. of not greater than about 0.16, and in certain embodiments,not greater than 0.158. In even further embodiments, the foam exhibitsan initial k-factor (BTU in/hr ft²° F.) at 110° F. of not greater thanabout 0.18, and in certain embodiments, not greater than 0.1772. Whilenot limited thereto, such a foam may be a rigid foam, open cell foam,closed cell foam, flexible foam or an integral skin foam. It may also bea pray applied foam or a pour-in-place foam. It may also be incorporatedinto an article or otherwise in an article or apparatus, such as, butnot limited to, a refrigerator or freezer.

Additional embodiments and advantages to the present invention will bereadily apparent based on the disclosure provided herein.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates a comparison of initial k-factors for1,1,1,4,4,4-hexafluorobutene (1336mzzm),E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and blends of1,1,1,4,4,4-hexafluorobutene (1336mzzm) andE-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

FIG. 2 illustrates a comparison for percent increase in k-factor after a14 day aging period for 1,1,1,4,4,4-hexafluorobutene (1336mzzm),E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and blends of1,1,1,4,4,4-hexafluorobutene (1336mzzm) andE-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

FIG. 3 illustrates a comparison of an 14 day k-factor for1,1,1,4,4,4-hexafluorobutene (1336mzzm),E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and blends of1,1,1,4,4,4-hexafluorobutene (1336mzzm) andE-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

FIG. 4 illustrates a comparison of an 8 day k-factor for1,1,1,4,4,4-hexafluorobutene (1336mzzm),E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and blends of1,1,1,4,4,4-hexafluorobutene (1336mzzm) andE-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to mixtures comprising, consisting essentially ofor consisting of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and1-chloro-3,3,3-trifluoropropene (1233zd). As noted above, the use of1336mzzm does not meet all the ideal requirements of a blowing agent,most notably because of its boiling point, high molecular weight, andprohibitive cost of production. The present invention has surprising andunexpectedly found that the addition of 1233zd, particularly the transisomer, as a co-blowing agent reduces the blowing agent cost but moreimportantly provides unexpected substantial improvement to the thermalperformance of foams prepared with the blend.

As used herein the term “1,1,1,4,4,4-hexafluorobutene” or “1336mzzm”generally refers to either or both the the cis- or trans-form. The terms“cis HFO-1336mzzm” and “trans HFO-1336mzzm” are used herein to describethe cis- and trans-forms of 1,1,1,4,4,4-hexafluorobutene, respectively.The terms “1,1,1,4,4,4-hexafluorobutene” or “1336mzzm” therefore includewithin its scope cisHFO-1336mzzm, transHFO-1336mzzm, and allcombinations and mixtures of these. In preferred embodiments, 1336mzzmrefers to the cis isomer. The present invention, however, is not limitedthereto and may include only trans-1336mzzm or mixtures of the cis andtrans isomers. In further embodiments, the 1336mzzm may include fromabout 50 weight percent to about 100 weight percent of the cis isomerand from about 0 weight percent to about 50 weight percent of the transisomer; from about 75% weight percent to about 100 weight percent of thecis isomer and from about 0 weight percent and 25 weight percent of thetrans isomer; or from about 90 weight percent to about 100 weightpercent of the cis isomer and from about 0 weight percent to about 10weight percent of the trans isomer. Such ranges for the composition of1336mzzm are not necessarily limiting to the instant invention and maybe also be provided in any effective amount to achieve the advantagesprovided herein.

As used herein the term “1-chloro-3,3,3-trifluoropropene” or “1233zd”generally refers to either or both the cis- or trans-form. The terms“cis HCFO-1233zd” and “trans HCFO-1233zd” are used herein to describethe cis- and trans-forms of 1,1,1-trifluo,3-chlororopropene,respectively. The terms “1-chloro-3,3,3-trifluoropropene” or “1233zd”therefore include within its scope cisHCFO-1233zd, transHCFO-1233zd, andall combinations and mixtures of these. In preferred embodiments, 1233zdrefers to the trans isomer. The present invention, however, is notlimited thereto and may include only cis-1233zd or mixtures of the cisand trans isomers. In further embodiments, the 1233zd may include fromabout 50 weight percent to about 100 weight percent of the trans isomerand from about 0 weight percent to about 50 weight percent of the cisisomer; from about 75 weight percent to about 100 weight percent of thetrans isomer and from about 0 weight percent to about 25 weight percentof the cis isomer; or from about 90 weight percent to about 100 weightpercent of the trans isomer and from about 0 weight percent to about 10weight percent of the cis isomer. Such ranges for the composition of1233zd are not necessarily limiting to the instant invention and may bealso be provided in any effective amount to achieve the advantagesprovided herein.

The amount of 1336mzzm and 1233zd, contained in the present compositionscan vary widely, depending the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present invention. Moreover, thecompositions of the present invention can be azeotropic, azeotrope-likeor non-azeotropic. In certain embodiments, the compositions comprisefrom about 5 to about 70 mole percent 1336mzzm and from about 30 toabout 95 mole percent 1233zd. In further non-limiting embodiments, thecompositions comprise from about 30 to about 70 mole percent 1336mzzmand from about 30 to about 70 mole percent 1233zd; from about 40 toabout 60 mole percent 1336mzzm and from about 40 to about 60 molepercent 1233zd; or about 50 mole percent 1336mzzm and about 50 molepercent 1233zd.

While the compositions of 1336mzzm and 1233zd may be provided as ablowing agent composition, additional components or adjuvants may beprovided and include, but are not limited to co-blowing agent(s),polyol(s), surfactant(s), polymer modifier(s), colorant(s), dye(s),solubility enhancer(s), flammability suppressant(s), flameretardants(s), antibacterial agent(s), viscosity reduction modifier(s),filler(s), vapor pressure modifier(s), nucleating agent(s), catalyst(s)and combination of any two or more of these. Alternative co-blowingagents may also be provided.

In one embodiment, such co-blowing agents may include one or morehydrocarbons or hydrofluorocarbons (HFCs), particularly C4-C6hydrocarbons or C1-C4 HFCs, that are known in the art. Examples of suchHFC co-blowing agents include, but are not limited to, one or acombination of difluoromethane (HFC-32), fluoroethane (HFC-161),difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane(HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245),hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea),pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all isomersof all such HFC's. With respect to hydrocarbons, the present blowingagent compositions also may include in certain preferred embodiments,for example, iso, normal and/or cyclopentane for thermoset foams andbutane or isobutane for thermoplastic foams. Other materials, such aswater, CO₂, CFCs (such as trichlorofluoromethane (CFC-11) anddichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such asdichloroethylene (preferably trans-dichloroethylene), ethyl chloride andchloropropane), HCFCs, C1-C5 alcohols (such as, for example, ethanoland/or propanol and/or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4ethers (including ethers (such as dimethyl ether and diethyl ether),diethers (such as dimethoxy methane and diethoxy methane)), and methylformate, organic acids (such as but not limited to formic acid),including combinations of any of these may be included, although suchcomponents not necessarily preferred in many embodiments due to negativeenvironmental impact. The relative amount of any of the above notedadditional co-blowing agents, as well as any additional components whichmay be included in present compositions, can vary widely within thegeneral broad scope of the present invention according to the particularapplication for the composition, and all such relative amounts areconsidered to be within the scope hereof.

One aspect of the present invention provides foamable compositions. Asis known to those skilled in the art, foamable compositions generallyinclude one or more components capable of forming foam. As used herein,the term “foam forming agent” is used to refer to a component, or acombination on components, which are capable of forming a foamstructure, preferably a generally cellular foam structure. The foamablecompositions of the present invention include such component(s) and ablowing agent blend, e.g. a blend including at least 1336mzzm and1233zd.

Foams and foamable compositions of the instant invention relategenerally to all foams, (including but not limited to closed cell foam,open cell foam, rigid foam, flexible foam, integeral skin and the like),prepared from a foam formulation containing a blowing agent compositionof the invention. Applicants have found that one advantage of the foamsis the ability to achieve exceptional thermal performance under lowtemperature conditions, as evidence from the k-factor data providedherein. Although it is contemplated that the present foams may be usedin a wide variety of applications, in certain preferred embodiments thepresent invention comprises appliance foams in accordance with thepresent invention, including refrigerator foams, freezer foams,refrigerator/freezer foams, panel foams, and other cold or cryogenicmanufacturing applications.

In certain embodiments, the one or more components capable of formingfoam comprise a thermosetting composition capable of forming foam and/orfoamable compositions. Examples of thermosetting compositions includepolyurethane and polyisocyanurate foam compositions, and also phenolicfoam compositions. This reaction and foaming process may be enhancedthrough the use of various additives such as catalysts and surfactantmaterials that serve to control and adjust cell size and to stabilizethe foam structure during formation. Furthermore, is contemplated thatany one or more of the additional components described above withrespect to the blowing agent compositions of the present invention couldbe incorporated into the foamable composition of the present invention.In such thermosetting foam embodiments, one or more of the presentcompositions are included as or part of a blowing agent in a foamablecomposition, or as a part of a two or more part foamable composition,which preferably includes one or more of the components capable ofreacting and/or foaming under the proper conditions to form a foam orcellular structure.

With respect to the preparation of rigid or flexible polyurethane orpolyisocyanurate foams using the foregoing as the blowing agent, any ofthe methods well known in the art can be employed. See Saunders andFrisch, Volumes I and II Polyurethanes Chemistry and Technology (1962).In general, polyurethane or polyisocyanurate foams are prepared bycombining an isocyanate, a polyol or mixture of polyols, a blowing agentor mixture of blowing agents, and other materials such as catalysts,surfactants, and optionally, flame retardants, colorants, or otheradditives.

It is convenient, though not exclusive, in many applications to providethe components for polyurethane or polyisocyanurate foams in pre-blendedfoam formulations. Most typically, the foam formulation is pre-blendedinto two components. The isocyanate or polyisocyanate compositioncomprises the first component, commonly referred to as the “A”component. The polyol or polyol mixture, surfactant, catalysts, blowingagents, flame retardant, and other isocyanate reactive componentscomprise the second component, commonly referred to as the “B”component. While the surfactant, catalyst(s) and blowing agentcomposition are usually placed on the polyol side, they may be placed oneither side, or partly on one side and partly on the other side.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix, forsmall preparations, or preferably machine mix techniques to form blocks,slabs, laminates, pour-in-place panels and other items, spray appliedfoams, froths, and the like. Optionally, other ingredients such as fireretardant, colorants, auxiliary blowing agents, water, and even otherpolyols can be added as a third stream to the mix head or reaction site.Most conveniently, however, they are all incorporated into one Bcomponent.

Any organic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Preferred, as a class is the aromatic polyisocyanates.Preferred polyisocyanates for rigid polyurethane or polyisocyanuratefoam synthesis are the polymethylene polyphenyl isocyanates,particularly the mixtures containing from about 30 to about 85 percentby weight of methylenebis(phenyl isocyanate) with the remainder of themixture comprising the polymethylene polyphenyl polyisocyanates offunctionality higher than 2. Preferred polyisocyanates for flexiblepolyurethane foam synthesis are toluene diisocyanates including, withoutlimitation, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, andmixtures thereof.

Typical polyols used in the manufacture of rigid polyurethane foamsinclude, but are not limited to, aromatic amino-based polyether polyolssuch as those based on mixtures of 2,4- and 2,6-toluenediamine condensedwith ethylene oxide and/or propylene oxide. These polyols find utilityin pour-in-place molded foams. Another example is aromaticalkylamino-based polyether polyols such as those based on ethoxylatedand/or propoxylated aminoethylated nonylphenol derivatives. Thesepolyols generally find utility in spray applied polyurethane foams,though such use is not considered limiting to the invention and may beadapted as otherwise understood in the art or provided herein. Anotherexample is sucrose-based polyols such as those based on sucrosederivatives and/or mixtures of sucrose and glycerine derivativescondensed with ethylene oxide and/or propylene oxide. These polyolsgenerally find utility in pour-in-place molded foams, again such use isnot considered limiting to the invention and may be adapted as otherwiseunderstood in the art or provided herein.

Typical polyols used in the manufacture of flexible polyurethane foamsinclude, but are not limited to, those based on glycerol, ethyleneglycol, trimethylolpropane, ethylene diamine, pentaerythritol, and thelike condensed with ethylene oxide, propylene oxide, butylene oxide, andthe like. These are generally referred to as “polyether polyols”.Another example is the graft copolymer polyols, which include, but arenot limited to, conventional polyether polyols with vinyl polymergrafted to the polyether polyol chain. Yet another example is polyureamodified polyols which consist of conventional polyether polyols withpolyurea particles dispersed in the polyol.

Examples of polyols used in polyurethane modified polyisocyanurate foamsinclude, but are not limited to, aromatic polyester polyols such asthose based on complex mixtures of phthalate-type or terephthalate-typeesters formed from polyols such as ethylene glycol, diethylene glycol,or propylene glycol. These polyols are used in rigid laminatedboardstock, and may be blended with other types of polyols such assucrose-based polyols, and used in polyurethane foam applications.

Catalysts used in the manufacture of polyurethane foams are typicallytertiary amines including, but not limited to, N-alkylmorpholines,N-alkylalkanolamines, N,N-dialkylcyclohexylamines, and alkylamines wherethe alkyl groups are methyl, ethyl, propyl, butyl and the like andisomeric forms thereof, as well as heterocyclic amines. Typical, but notlimiting, examples are triethylenediamine, tetramnethylethylenediamine,bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine,tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine,piperazine, N,N-dimethylcyclohexylamine, N-ethylmorpholine,2-methylpiperazine, N,N-dimethylethanolamine, tetramethylpropanediamine,methyltriethylenediamine, and mixtures thereof.

Optionally, non-amine polyurethane catalysts are used. Typical of suchcatalysts are organometallic compounds of lead, tin, titanium, antimony,cobalt, aluminum, mercury, zinc, nickel, copper, manganese, zirconium,bismuth, and mixtures thereof. Exemplary catalysts include, withoutlimitation, lead 2-ethylhexoate, lead benzoate, ferric chloride,antimony trichloride, and antimony glycolate. A preferred organo-tinclass includes the stannous salts of carboxylic acids such as stannousoctoate, stannous 2-ethylhexoate, stannous laurate, and the like, aswell as dialkyl tin salts of carboxylic acids such as dibutyl tindiacetate, dibutyl tin dilaurate, dioctyl tin diacetate, and the like.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art including, but not limited to, glycine salts andtertiary amine trimerization catalysts, alkali metal carboxylic acidsalts, and mixtures thereof. Preferred species within the classes arepotassium acetate, potassium octoate, andN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Dispersing agents, cell stabilizers, and surfactants may be incorporatedinto the blowing agent mixture. Surfactants, better known as siliconeoils, are added to serve as cell stabilizers. Some representativematerials are sold under the names of DC-193, B-8404, and L-5340 whichare, generally, polysiloxane polyoxyalkylene block co-polymers such asthose disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458.

Other optional additives for the blowing agent mixture may include flameretardants such as tris(2-chloroethyl) phosphate, tris (2-chloropropyl)phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl)phosphate, diammonium phosphate, various halogenated aromatic compounds,antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.Other optional ingredients may include from 0 to about 3 percent water,which chemically reacts with the isocyanate to produce carbon dioxide.The carbon dioxide acts as an auxiliary-blowing agent.

Generally speaking, the amount of the blowing agent composition presentin the blended mixture is dictated by the desired foam densities of thefinal polyurethane or polyisocyanurate foams products. The polyurethanefoams produced can vary in density from about 0.5 pound per cubic footto about 40 pounds per cubic foot, preferably from about 1.0 to about20.0 pounds per cubic foot, and most preferably from about 1.5 to about6.0 pounds per cubic foot for rigid polyurethane foams and from about1.0 to about 4.0 pounds per cubic foot for flexible foams. The densityobtained is a function of how much of the blowing agent, or blowingagent mixture, is present in the A and/or B components, or that is addedat the time the foam is prepared.

In another embodiment, the mixtures and compositions of this inventionmay be used as propellants in sprayable compositions, either alone or incombination with known propellants. The sprayable composition comprises,consists essentially of, and consists of a material to be sprayed and apropellant comprising, consisting essentially of, and consisting of amixture or composition of the invention. Inert ingredients, solvents,and other materials may also be present in the sprayable mixture.Preferably, the sprayable composition is an aerosol. Suitable materialsto be sprayed include, without limitation, cosmetic materials such asdeodorants, perfumes, hair sprays, cleansers, and polishing agents aswell as medicinal materials such as anti-asthma and anti-halitosismedications and metered dose inhalers (MDIs).

The compositions of the invention may also be used in a method ofdissolving a contaminant or removing a contaminant from the surface of asubstrate that comprises, consists essentially of, and consists of thestep of contacting the substrate with the compositions of the presentinvention.

The foams in accordance with the present invention, in certain preferredembodiments, provide one or more exceptional features, characteristicsand/or properties, including: thermal insulation efficiency(particularly for thermoset foams), dimensional stability, compressivestrength, aging of thermal insulation properties, all in addition to thelow ozone depletion potential and low global warming potentialassociated with many of the preferred blowing agents of the presentinvention. In certain highly preferred embodiments, the presentinvention provides thermoset foam, including such foam formed into foamarticles, which exhibit improved thermal conductivity relative to foamsmade using the same blowing agent (or a commonly used blowing agentHFC-245fa) in the same amount but without the blowing agent compositionof the present invention. In certain highly preferred embodiments, thethermoset foams, and preferably polyurethane foams, of the presentinvention exhibit an initial k-factor (BTU in/hr ft²° F.) at 40° F. ofnot greater than about 0.14, more preferably not greater than 0.138.Furthermore, in certain embodiments, it is preferred that the thermosetfoams, and preferably the polyurethane foams of the present inventionexhibit an initial k-factor (BTU in/hr ft²° F.) at 75° F. of not greaterthan about 0.16, more preferably not greater than 0.158. In even furtherembodiments, it is preferred that the thermoset foams, and preferablythe polyurethane foams of the present invention exhibit an initialk-factor (BTU in/hr ft²° F.) at 110° F. of not greater than about 0.18,more preferably not greater than 0.1772.

The following examples are provided for the purpose of illustrating thepresent invention but without limiting the scope thereof.

EXAMPLES

Foams with 1336mzzm, 1233zd(E), 30/70 mole % blend of 1233zd(E)/1336mzzmand 70/30 mole % blend of 1233zd(E)/1336mzzm as blowing agent wereprepared. The polyol master batch composition is shown in Table 1 whilethe generic spray foam formulations with corresponding amounts ofblowing agents are listed in Table 2. The foams were prepared with and 3second pour time and 8 second mix time. The raw materials temperatureswere 50 OF polyol/70° F. MDI.

TABLE 1 Polyol Master Batch Composition Component Lot Numbers php Manichpolyether polyol, OH 470 VC03019501 50.00 Aromatic polyester polyolMY4020-18 43.75 Diethylene glycol B11 + 024 6.25 Silicone surfactant0001580875 1.25 Dimethyl ethanol amine 258009 2.00 Neutral chlorinatedphosphate ester 122 12.50 Water 1.25 Total 117.00

TABLE 2 Generic Spray Foam Formulations 1233zd(E)/1336mzzm1233zd(E)/1336mzzm 1233zd(E) 70/30 mole % 30/70 mole % 1336mzzm Mol. %of 1336mzzm 0 30 70 100 Mol. % of 1233zd(E) 100 70 30 0 Moles of1336mzzm 0 0.061 0.143 0.204 Moles of 1233zd(E) 0.204 0.143 0.061 0Polyol Blend Master Batch 117.0 117.0 117.0 117.0 1336mzzm 0 10.0 23.533.5 1233zd(E) 26.5 18.6 7.9 0 Total 143.5 145.6 148.4 150.5 IsocyanatePolymeric MDI 137.38 137.38 137.38 137.38 (NCO 31.5 wt. %) NCO Index 110110 110 110

Physical Properties—Reactivity

The relationship between cream time, gel time and tack free time areanticipated. They are equivalent for all foams prepared.

TABLE 3 Foam Reactivity 1233zd(E)/1336mzzm 1233zd(E)/1336mzzm 1233zd(E)70/30 mole % 30/70 mole % 1336mzzm Reactivity, second 10-24-1 10-24-310-24-2 10-23-2 Cream Time 15 15 12 12 Gel Time 35 34 33 38 Tack-FreeTime 45 45 44 48

The foams prepared were well mixed and equivalent in quality. The blockdensity of the foams produced is similar as is the ratio of block tocore density. This is anticipated since the foams were prepared withequivalent moles of blowing agents.

TABLE 4 Foam Quality: Density 1233zd(E)/1336mzzm 1233zd(E)/1336mzzm1233zd(E) 70/30 mole % 30/70 mole % 1336mzzm Density, lb/ft³ 10-24-110-24-3 10-24-2 10-23-2 Foam Density-Block* 1.8 1.78 1.81 1.79 FoamDensity-Core* 1.83 1.71 1.77 1.82 Ratio Block/Core Density 0.98 1.041.02 0.98 *Block density is density of the squared foam prior to samplecutting. Core density is density of the k-factor sample taken from themiddle of the sample

Thermal Conductivity

Initially, foam produced with 1336mzzm show the non-linear curve shapenormally found with high boiling blowing agents. This is attributed tothe condensation of the blowing agent in the foam matrix at temperaturesbelow the boiling point of the blowing agent. It is unanticipated thatthe 30/70 mole % 1336mzzm/1233zd(E) and 70/30 mole %1336mzzm/1233zd(E)blend does not show the same curve shape since this isnot an azeotropic composition. In addition the thermal conductivity offoams prepared with these blends are significantly improved over thosemade with 1233zd(E). Not only are they improved, the improvement isnonlinear in relationship to the amount of 1336mzzm added to the blowingagent blend. It is particularly interesting that the improvement at thelow mean temperatures is significant and not 1233zd(E) concentrationdependant. In addition, it is notable that the foam prepared from theblends age slower than the 1233zd(E) and the 1336mzzm foams.

TABLE 5 Foam Thermal Conductivity 1233zd(E)/ 1233zd(E)/ 1336mzzm1336mzzm 1233zd(E) 70/30 mole % 30/70 mole % 1336mzzm 10-24-1 10-24-310-24-2 10-23-2 Initial 40° F. 0.1357 0.1328 0.1320 0.1356 75° F. 0.15400.1485 0.1459 0.1432 110° F.  0.1744 0.1667 0.1643 0.1612 8 Day 40° F.0.1415 0.1360 0.1367 0.1397 75° F. 0.1595 0.1527 0.1506 0.1472 110° F. 0.1798 0.1719 0.1711 0.1672 14 Day 40° F. 0.1431 0.1371 0.1380 0.142175° F. 0.1626 0.1558 0.1505 0.1479 110° F.  0.1838 0.1772 0.1697 0.1667

What is claimed is:
 1. A blowing agent composition comprising:1,1,1,3,3,3-hexafluorobutene (1336mzzm); 1-chloro-3,3,3-trifluoropropene(1233zd); and optionally at least one adjuvant selected from the groupconsisting of co-blowing agent(s), polyol(s), surfactant(s), polymermodifier(s), colorant(s), dye(s), solubility enhancer(s), flammabilitysuppressant(s), flame retardants(s), antibacterial agent(s), viscosityreduction modifier(s), filler(s), vapor pressure modifier(s), nucleatingagent(s), catalyst(s) and combination of any two or more of these. 2.The blowing agent of claim 1 wherein said1-chloro-3,3,3-trifluoropropene (1233zd) comprisestrans-1-chloro-3,3,3-trifluoropropene.
 3. The blowing agent of claim 1wherein said 1-chloro-3,3,3-trifluoropropene (1233zd) comprises fromabout 50 weight percent to about 100 weight percenttrans-1-chloro-3,3,3-trifluoropropene and from about 0 weight percent toabout 50 weight percent cis-1-chloro-3,3,3-trifluoropropene.
 4. Theblowing agent of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene(1233zd) comprises from about 75 weight percent to about 100 weightpercent trans-1-chloro-3,3,3-trifluoropropene and from about 0 weightpercent to about 25 weight percent cis-1-chloro-3,3,3-trifluoropropene.5. The blowing agent of claim 1 wherein said1-chloro-3,3,3-trifluoropropene (1233zd) comprises from about 90 weightpercent to about 100 weight percenttrans-1-chloro-3,3,3-trifluoropropene and from about 0 weight percent toabout 10 weight percent cis-1-chloro-3,3,3-trifluoropropene.
 6. Theblowing agent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene(1336mzzm) comprises cis-1,1,1,3,3,3-hexafluorobutene.
 7. The blowingagent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene (1336mzzm)comprises from about 50 weight percent to about 100 weight percentcis-1,1,1,3,3,3-hexafluorobutene and from about 0 weight percent toabout 50 weight percent trans-1,1,1,3,3,3-hexafluorobutene.
 8. Theblowing agent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene(1336mzzm) comprises from about 75 weight percent to about 100 weightpercent cis-1,1,1,3,3,3-hexafluorobutene and from about 0 weight percentto about 25 weight percent trans-1,1,1,3,3,3-hexafluorobutene.
 9. Theblowing agent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene(1336mzzm) comprises from about 90 weight percent to about 100 weightpercent cis-1,1,1,3,3,3-hexafluorobutene and from about 0 weight percentto about 10 weight percent trans-1,1,1,3,3,3-hexafluorobutene.
 10. Theblowing agent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene isprovided in an amount from about 5 to about 70 mole percent and said1-chloro-3,3,3-trifluoropropene is provided in an amount from about 30to about 95 mole percent.
 11. The blowing agent of claim 1 wherein said1,1,1,3,3,3-hexafluorobutene is provided in an amount from about 30 toabout 70 mole percent and said 1-chloro-3,3,3-trifluoropropene isprovided in an amount from about 30 to about 70 mole percent.
 12. Theblowing agent of claim 1 wherein said 1,1,1,3,3,3-hexafluorobutene isprovided in an amount from about 40 to about 60 mole percent and said1-chloro-3,3,3-trifluoropropene is provided in an amount from about 40to about 60 mole percent.
 13. The blowing agent of claim 1 wherein said1,1,1,3,3,3-hexafluorobutene is provided in an amount of about 50 molepercent and said 1-chloro-3,3,3-trifluoropropene is provided in anamount of about 50 mole percent.
 14. The blowing agent of claim 1wherein said adjuvant comprises at least one co-blowing agent selectedfrom the group consisting of water, CO₂, CFCs, HCCs, HCFCs, C1-C5alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers and diethers,organic acids, and combinations of two or more of these.
 15. The blowingagent of claim 1 wherein said adjuvant comprises water as at least oneco-blowing agent.
 16. A foamable composition comprising a foam formingagent and the blowing agent composition of claim
 1. 17. The foamablecomposition of claim 16 wherein the foamable composition exhibits aninitial k-factor (BTU in/hr ft²° F.) at 40° F. of not greater than about0.14.
 18. A foam premix composition comprising polyol and the blowingagent composition of claim
 1. 19. A method of forming a foam comprisingadding to foaming composition the blowing agent composition of claim 1.20. A foam comprising a plurality of polymeric cells and the blowingagent composition of claim 1.